Tin ore treatment



G. GUTZEIT ETAL TIN ORE IREATMENT 2 Sheets-Sheet 1 Fle d Jan. 23, 1943 ATTORNEY Jan; 7, 1947.

G. GUTZEIT ET A L TIN ORE TREA'IMENT Filed Jan. 23, 1945 2 Sheets-Sheet 2 TEMPERATURE OF THE REDUGING ROAST(F) FIG.2.

INV\ENT.ORS GREGOIRE GUTZEIT, ELLIOTT J.R'OBERTS a. ROBERT B.THOMPSON Patented Jan. 7, 1947 TIN ORE TREATMENT Gregoire Gutzeit and Elliott J. Roberts, Westport,

and. Robert B. Thompson, Wilton, Conn, assignors to The Dorr Company, New York, N. Y., a corporation of Delaware Application J anuary 23, 1943, Serial No. 473,406

6 Claims.

This invention relates to the recovery of tin and metals of the same class rom ores and mill products. It renders specally possible the extraction of tin trom refractory ores (complex cassterite-sulphide ores and ores containing socalled collodal tin) as well as from the tailings of tin concentrators, although it is not applicable to ores with a carbonate gangue.

Tin occurs principally as the mineral cassiterite, S1102. As is well known to mining engineers, there are two main types of tin ores: the first one is the socalled stream tin, i. e., an alluvial deposit where the cassiterite particles are generally tree; the other type is the 10de tin, in which the tn oxide is mcstly associated with stannite (tin copper sulphide), pyrites, arsenopyrites, bismuth, antimony, and arsenic sulphides, and often with wolframite. A rarer occurrence is the eluvial tin (French Indo-China, Belgian Congo). The ores of the first types generally yield clean concentrates and fairly good tailings. These are principally found in the Malaya Peninsula and in the Netherland Indies (Banka and Billiton). The second type is more scattered over the world, and is found mainly in Bolivia, Nigeria, Belgian Congo, Cornwall (England), Brittany (France) China, and Indo-China. This type of ore is difficult to concentrate. The l0sses in the concentration tailings are alWays very high, especially in the slime fraction where grades of 2.5% Sn and. over are not rare. The sulphdes are often floated out of the crude ore, but even so the tailings and concentrates stil1 contain mor or less base-metal sulphides. In the smelting plant, the concentrates have to be roasted,

sometimes recleaned by gravity methods, and leached with hydrocnloric acid in order to remove the impurities (excess of iron) prior to the smelting operation proper.

The object of this invention is to recover the tin lost in these concentrator tailngs, or even to treat directly the refractory ores as well as any suitable mill product.

Many attempts have been made to leach the tin directly from its ores or rom concentrates but these have all failed due to the fact that cassiterite is completely insoluble in all aqueous solutions. (Mantell, Tin (1929) A. C. S. Monograph Series, pp. 131-138.) 'I'his invention proposes to make use of severa1 important and. conjoint stages of treatment of which the first is a reducing sulphidizing raast which results, under critical conditions, in the formation of a soluble tin compound. The secohd stage comprises cooling the roasted material under nonoxidizing conditions, and the third stage comprises a leaching operation whereby a tin-hearing solution is selectively obtained that can be separated from the gangue residue. Another stage comprises precipitating the tin out of its mother liquor under criti'cal conditions.

Since it is the tin that is the value to be recovered and since the proportion thereof in the ore or other material is small, a high percentage of extraction of the tin is a feature of advantage of this invention. Since tin ore is normally ound only in out of the way places in the world, where freight rates are high, the availability of chernical reagents is very important. Another feature of advantage in this invention is the possibility of regeneration of the reagent for reuse.

As the roasting stage: If one attempts to reduce the cassiterite of a tin ore which has a substantial content of iron compounds as well as other base metals in some proportion, the difficulty is faced in that in the process of reducing the tin, iron and/or certain other elements are likely to be reduced to the metallic state. A1- loys of the tin and these metals then form and no economicai method has yet been found or leaching out tin so alloyed. Therefore, the first object of the roast of this nvention is to reduce the tin compound while not reducing the iron, so that the reduced tin compound is made available or subsequent leaching. T0 that end this invention proposes to use a sulphidizing atmosphere whereby the tin oxide of the ore or ore matera1 is converted rom tin oxide principally to stannous sulphide (SnS) which is soluble in a subsequent leaching process. What is perhaps of eq1lal importance, is that the iron and certain other elements are held as, or are convertedto, sulphides, trom which combination they do not so readily reduce to the metallic state.

The requirements of this suiphidizing roast are that first it must be carried out in an atmosphere of reducing gas such as hydrogen and enough sulphur should be present to convert the tin and possible interfering elements to their sulphides. The sulphur needed is preferably evolved in situ, although it may be added as a gas if desired. The temperature of the Toast is important, because if too 10W, the requisite reactions do not take place, while if too high, tin may be lost through volatilization. Sui1cient time must be allowed to convert the major part of the tin into the sulphidc, but too long a reaction time should be avoided due to the danger of ormation of metallic iron or other metal which would alloy with any metallic tin which may be formed during the process. This is especially true when the sulphur supply is marginal or inadequate. It is practically impcssible and is also unnecessary to entirely prevent the rormation of metallic tin as long as the alloying metals are prevented rom appearing.

Thus the requirements of the roast include the presence of a proper amount of sulphur and a reducing gas as well as temperatures within a critical range and a certain control of the time interval of heating. The ore or mi1l product to be so roasted should be properly sub-divided as to particle size, which should preferably not be in excess of 65 mesh and in general the smaller the particle size the better if the process is to be eficient.

The temperature range should be aoove 55) C. and below 900 C. with optimum between 650 C. and 830 0. The amount of sulphur present should be substantially over the theoretical chemical requirements thereof to accomplish the reaction and the amount of hydrogen or other strongly reducing gas should always be suficient to assure the reducing action.

As to the cooling stage, the roasted, treated and converted. tin-hearing material should be cooled under nomoxidizing conditions. A variety of cooling methods can be used so long as the reduced constituents of the ore are not permitted to have any substantial reversion due to oxidation.

As to the leaching stage, the essential characteristic of this treatment is that the cooled, reduced and sulphidized ore material is subjected to the tin sulphicle leaching action of a caustic alkali such as caustic soda (NaOH) Th reason for this is that the tin sulphide and metallic tin are soluble in alkali whereas the gangue materials, including the iron and copper compounds, arenot. So the purpose of the leaching stage is to dissolve selectively the tin compound out of the ore material, whereupon the tin compounds in solution are readily separable from the solid gangue residue.

As to the precipitation stage, the tin solution is subjectecl to the action of a precipitation agent such as calcium, barium, strontium or magnesium sa1t but preferably lime. Here, however, a requisite is that precipitation shall take place in a relatively high concentration of already precipitated soiid phase of calcium-tin compounds, probabiy calcium orthostannate. Uniess this precaution is used, a much larger amount of 1ime is needed, indeeol as much as 30) percent of theoretical and then the precipitate yielded is W in grade, very finely divided ancl difficult of separation. On the other hand, if the precipitation is carried out in the presence of a high concentration or pulp blanket of already precipitated stannate, the precipitated particles are coarse crystals with a rapid settling rate and the solution is cornpletely stripped of tin with only the theoretical quantity of lme. 'Ihs means that they not only wil1 settle quickly in th mother liquor, but are readily fiiterable therefrom. The separated mother liquor or filtrate which is a harren solution, is then available for recirculation and reuse as a solvent in the leaching stage.

After filtration ancl drying the stannate is preferably calcined to drive out the combined water, forming anhydrous calcium orthostannate, since in this form the product may be stripped more eeonomically.

If a tin ore or a tin-hearing mill product such as tailings, is submitted, properly subdivided as to particle size, to the treatment as summarized above, and if the roasted products are leached in a waak sodium hydroxide solution, the curve of recovered tin plotted as a function of the roasting temperature for a specific time interval wil] show a maximum indicating a critical temperature range, which curve falls away and also shows that undesirable reactions result if the temperature is too high.

As already stated, the tin-hearing 10de ores always contain sulphides, and mainly pyrite. Pyrite (FeS2) decomposes into pyr1hotte (FeSw) at a temperature a'oove 575 C. The reaction is very rapid at 665 C. In the presence of hydro gen, .however, the decomposition of pyrite starts at a lower temperature. Thus, the sulphur for the reaction is furnished in Bolivian tin ore by the alteration of pyrite to pyrrhotite which pyrite or its sulphur-hearing equivalent is added to the ore to supply any lack of natural constituent frorn which sulphur vvill evo1ve in situ, and the series of reactions involved may be represented by the follovving equations:

If the reduction is performed with hydrogen in th presence of pyrite or other sulphur evolving constituent from which sulphur is volatilized at a temperature lower than the temperature of the main reaction, the equation may be written in summarized form as ollows:

The use of a large excess of pyrite is objectionabie, so its use must be carefully controlled.

These reactions occur only abov e 550 C. Above 900 C. the tin sulphide volatilizes badly. Stannous sulphide, as already stated, is soluble in alkalis provided some oxidizing compound such as air be present. Stannous su1phide is further slowly reduced by the hydrogen to metallic tin- SIIS+H2=SIJ+H2S. Pure metallic tin is also soluble in sodium hydroxide in the presence of an oxidizing agent. Hovvever, in the presence of reduced metals (Cu, Bi, Fe, etc.) the metallic tin wil] form al1oys which are insoluble in alkalis.

These reactiong are not separate as in the systematic description above, but take place simultaneously at different rates. In fact, just above the reaction temperature, SnSz is possibly formed besides SnS and some Sn. Moreover, the conditions in the furnace are also a function of the time. At the beginning, ther is an excess of sulphur present, and the sulphidizing reaction is at its maximum; but when most of the sulphur has been evolved and has reacted or escaped as hydrogen sulphide, this atmosphere becomes more and more reducing.

If the sulphur available is marginal or inadequate, it is still possible to obtain fair results by carefully controlling the degree of reducton more particularly as exemplified by the time. By holding the time of contact at the reaction temperature to a minimum which may be as 10W as 10 minutes or so, a reasonable recovery may often be obtained, whereas langer times of 30 minutes may result in drastic lowering of the extraction olctainable with the NaOH solution.

A possible explanation of this behavior is as follows; At 650 or 700 pyrite readily breaks down into pyrrhotite, FeSm, with the rest of the sulphur being liberated as S2 or converted into I-I2S. These compounds carry out the other reactions indicated and the rest is carried away. If then all of the ron is in the form of pyrrhotite and the tin in the form of 5118, we have an ideal setup. I more reducing gas is passed over the charge metallic tin may form, bui; metallic ron is prevented from orming for a long period because the FeS1.2 must be substantially converted to FeS- FGS1.2+.ZH2*FGS+ZH2S before any l5'eS is reduceol to metallic ron. It takes a large excess of H2 to so reduce the FeSr.z to FeS: of the order of 106-1000 mols of H2 per atom of sulphur removed, depencling on the temperature. If only a small amount of this buffering pyrrhotite is present, practical considerations may cause enough hydrogen to be used to overcome the margin of safety which the pyrrhotite affords and cause metallic ron to be iormed:

which will then quickly alloy with any tin it comes in contact with and tie this tin up as an alkali insoluble particle.

If a hydrocarbon gas is used to provide the reclucing atmosphere, the presence of steam as a catalyst for the cracking of the hydrocarbon is alrnost a requirement in order to yie1d high recoveries. From the roasting furnace there escapes volatilized S, H2S, ASH3, SoSs, etc. In some cases it may be advantageous to remove the stannite prior to the reducing treatment, by flotation, acid leaching, or chlorine leach, as this mineral directly orms an alkali-insoluble compound.

The next step is the cooling, Which should be done to a temperature below the melting point of tin (230 C.) and under careful control so that the ore is cooled and passed into the leaching so lution in such a way as to prevent re-oxidation of the reduced ore. The leaching solution is best an alkali, like sodium sulphide, potassium sulphide, potassium hydroxide, or sodium hydroxide, and

should not contain calcium ions (softwater).

From an econornical point of view, NaO--I seems to be the best suited dissolvent. The ore is agitatecl With a weak solution of sodium hydroxide (containing an excess of reagent, say about five times the amount of tin to be leached) for a period of time up to the order of hours. A counter-ourrent decantation system is advantageous.

The dissolution of tin compouncls in the caustic solution requires the presence of oxygen to convert the tin to the stannic condition in which state it is soluble in caustic. This oxygen can be supplied by contacting the solution with atmospheric air. I-Iowever, if air loe also used for agi tation purposes, care should be exereised to prevent the formation of appreciable amounts of sodium carbonate.

The chemical reactions of the dissolution are as follows:

The strength of sodium hydroxide to be used is not important, but the total amount of NaOI-I present should be high enough to provide oom plete dissolu-tion in a reasonalole time. Seven to eight per cent by weight of NaOI-I on the basis of the calcined ore (containing 2% Sn) gave excellent results. The dissolution wil1 ordinarily be conducted at whatever temperature normally obtains in the plant, but in special cases intentonal temperature adjustment may be indicated by simple tests.

The best means of recovering the tin is a precipitation procedure which makes use of the ad.- dition of lime. The tin is precipitated as hy drated calcium orthostannate, containing alumina and calcium carbonate as the principal impurities. The precipitation of the Sn should preferably be carried out in the presence of previously precipitated Sn, i. e. of a precipitate of calcium stannate produced in a ormer cycle, for otherwise a large excess of lime would be necessary, in order to strip the solutionof its Sn. If the theoretical amount of linie be added to the solution. it has been found that not more than 2% of the Sn is recovered, and it was necessary to go to 300% of theoretical to efiectively precipitate the tin. But, i the lime loe added to the solution in the presence of previously precipitated Sn, the calculated amount on the basis of CaSnO3 reduces the tin content of the solution to a very 10W value. As NazC0z builds up in the solutions through excess of CO2, a certain amount of lime is used in precipitatng, CaC0s. Thereore, a slight excess of lime over tin is actually used in practice.

Effecting the precipitation in the presence of a 2%;% suspension of previous precipitates from a concentration of 10 to 12 grams of tin per liter of solution has given excellent results. Such a step seems to scrub the solution of its supersaturation and lorings the solution into equilibrium. The stannate precipitate is sandy, it settles to a 10W density of say 64% solids, anci filters easily, Since no excess lirne is used, the mother liquor can be re-used without carbonation as it is alreacly substantially free of lime. However, if regeneration is necessary, it can be done by the use of sodium carbonate or carbon dioxide.

A very satisfactory apparatus fcr accomplishing this precipitation step, is a machine made and sold by The Dorr Company, Inc., of New York, as shown in United States of America Patent No. 2,259,221 to Daroy, Roberts and Weber. in this apparatus, the precipitant is added to the lower part of the machine wherein flocculation takes place in a zone contaning a sludge blanket. The sludge bianket rises to a level above a sludge collecting pocket frorn which the precipitate is drawn of, while clarified effluent overlies the sludge blanket and overflows from the upper section of the machine. The hydrated calcium orthostannate precipitate, which runs about 41% Sn, is then dewatered such as by filtering. It contains 5 molecules of crystallization water, which are expelled at about 5Gil C. or below yielding a calcined product with more than Sn. The latter may be direc-tiy smelted to recover the tin, or may be treated in various ways to arrive at the final metallic tin.

O-ther methods of recovering the dissolVed tin values from the alkaline leaching medium are possible and in certain cases may be economically more desirable. One of these is to carbonate the alkaline solution with a C2 containing gas in the presence of an electrolyte such as NaCl if the Solut0ns are rather dilute. In this case the" tin is precipitated as hydrated stai1nio oxide which may be separated, dried and calcined to yield a high-grande product. 01 892 may be used as -a precipitating agent. The remaining solution'is regenerated with a controllecl amountoi lime.

Direct electrolysis of the solution is alsoa possibility with theproductioh of electrolytic metal 7 which may be then melted down and cast into bars. The tin may also be precipitated from solution in the metallic state by means of zinc dust, preferably after deaerating. In this case, zinc hydroxide will also be separate and may be recovered separately.

Example 1 Fine s1ime tailings from the 'I'elamayu (Aramayo Company, Bolivia), containing 2.49% Sn (of which 10% as stannite and. the rest as cassiterite) as well as pyrites and other metallic sulphides, were heated in a rotary kiln to 799 C. The heating perod was 22 minutes in an atmosphere of hydrogen and water vapor, provided by saturation of the reducing gas in water heated to 51 C. The kiln was rapidly cooled and the ore ieached at a dilution of :1 with an 0.8% sodium hydroxide solution. After 20 hours, 70.04% of the tin contained in the ore was extracted. A second leach with a fresh solution containing 0.8% NaOH gave an additional recovery of 8.5%. Thus, the total recovery was 78.54

Example 2 Composite talings from the Telamayo Mine (Aramayo Company, Bolivia), containing 1.86% Sn and 4.5% S, prncipally as pyrite, was batch roasted in a rotary kiln to 7 99 C for 25 minutes in a current of hydrogen, and cooled in the same gas. The calcine containing 1.94 Sn, was leached with 20 gpl. NaOI-I solutions in a. cyclic test procedure simulating counter-current leaching and decantation, The pregnant solution were precipitated with lime in the presence of previously precipitated material and the harren solutions reused. The test was continued for cycles and an average extraction of 83% and 9, tin recovery as CaSn0s of around 80% was obtained. The final product aiter calcning containea 51.4% Sn. Smelting tests on the latter product with the addition of SO2 and F8203 gave high reco-veries of metallic tin.

Drawings acco-mpany ths specificatio-n for aiding in an understanding of the invention, in which Fig. 1 shows a graph based upon tests showing the critical temperature factor for two different time intervals (combined of course with the proper reducing and sulphidizing conditions) while Fig. 2 is a. diagrammatic flowsheet to indicate in general the sequence of machines or apparatus usable to p1actice the invention on a com. mercial scale.

In Fig. 2 of the drawings, I I indicates a furnace or kiln in which the ore is subjected to a reducingsulphidizing roast, to which furnace the ore 12 is fed together with a suitable reducing gas l3. The furnace may also have fed to it pyrite or other source of sulphur, but f pyrite be used, an excess of pyrite is detrimental in the leaching, so the quantity used should be carefully controlled. In the event that a tin ore to be treated has a suficient sulphur content naturally in it of course pyrite need not be added. From the furnace H, gaseous products E6 of the reaction are emitted in the form mainly of sulphur and hydrogen-sulphide but these will also contain other products such as ASH3, SbS3, and the iike. The hot solid reaction products are discharged from the furnace I into a cooling apparatus or station i'l' so that they will be cooled quickly in a manner to prevent or minmize their re-oxidation. From the cooling apparatus 11 the solid reaction product passes through pipe I and is subjected to a leaching treatment in a leaching station i9 which as shown in the diagram inludes an agitator. It is contemplated that this leaching station will contain suitable agitators, together with a succession of thickeners for practicing what is commonly known as counter-current decantation or counter-current leaching and decantation. The reaction product is subjectecl in the leaching station l9 to action thereon by an alkaline leaching solvent, such as sodium hydroxide, and in the leaching station the tin goes into solution. The solution pregnant with the dissolved tin passes as effluent from the leaching station I9 through pipe 20 into a, precpitation station 2I which is housed within a machine to which there is also supplied through pipe 22 a precipitating agent, such as the hydroxides, oxides or salts of calcium, barium, strontium, magnesium, or the like.

The precipitation station or machine 2I, in the preferrecl form is described in the aiorementioned patent, and includes within its tank an assembly 23 of rotatable flocculating paddles or blades, and a sludge receiving and collecting pocket 24 from which sludge is withdrawn through a pipe 25 and conducted to a filter 26 or other dewatering apparatus. The precipitatin agent preciptates or strips the tin out from the pregnant solution that enters the machine or tank 2I, and this solid precipitate is removed from the tank in the form of sludge that is dewatered on the filter 25. Filtercake from filter 26 passes to a, calciner station 21 from which calcium stannate 28 emerges suitable for smelting or other treatment for recovering its tin content.

So much for the direct steps. But the process of this invention can be carried out continuously and cyclically. 'Io that end. the mud or pulp that forms a sediment in the leaehing station or thickener 19 is raked to discharge whereupon it is conducted through pipe 29 to a, dewatering and washing or filter station 312. From ths filter, there are two discharges, namely, one by which the filter cake of mud or pulp from which the solution has been substantially removed passes to discard or waste as at 31, and the other is the alkali solution filtrate or leaching liquor containing some tin which passes through pipe 32 on its way back into the leaching station I9. Supernatant efiluent from the precipitation station 2| overfiows from the upper section thereof in the form of an alkali solution substantially harren of tin in solution, and is conducted through pipe 33 back to the leaching station IS].

Assuming now that an operator has a plant ready to start up and he wants to determine the quantities of materials to use; the non-carbonate tin ore or material is analyzed to determine the amount of volatilizable sulphur needed in the kiln. The ore usually comprises tin compounds, divided into a major portion of tin oxide and a minor portion of tin-sulphide complex. Other constituents are iron oxides and sulphides as well as silicates of various kinds. The tin, sulphur and reactible iron content is determined analytically. Then there is calcuiated the quantity of sulphur needed chemically to be equivalent to the tin and iron. In such a calculation it is best to figure the tin as SnS and the iron as FGS1.2. I insufiicient S is shown by the calculation, pyrite is added to make up the difference. It is apparent that there is available for tin and oxide iron compounds 0.8 atom of sulphur per mol of FeS2. some excess of sulphur above that so calculated makes the reduction less critical as to timing but too much is undesirable. This then comprises the burden of the kiln, and hydrogen or hydrogen 9 containing reducing gas is continually passed through the kln during the heat treatment stage when the tin oxide is converted to stannous sulphide while the sulphur minimizes reduction of iron compounds to metallic iron. As the resulting tin compounds are soluble in alkalis while the iron compounds are insoluble, an alkali leach causes the dissolving of the tin compounds, leaving the iron compounds as solid residue. Therefore, conjoint requirements for the practice of this inventionare exemplified, for instance, in the sulphidizing reducing roast treated at a reaction temperature within a specific range followed by alkali leaching, followed by a special precipitation stage if unusual efficiency is to be realized therein, and then calcination of the separate precipitated tin compound or other tin recovery step, with the leaching operation being cyclic.

We claim:

1. The process of treating tin ore, which comprses heating the ore during a controlled period of time above 550 and below 800 C. in a strongly reducing atmosphere and in the presence of enough sulphur so that stannous sulphide and metallic tin are ormed and so that the iron in the final product is in the form of its sulphide stable at the reaction temperature, and under such conditions to insure that tin sulphide is not volatilized; cooling saidtreated material under.

non-oxidizing conditions; leaching out; the treated material with a solution of an alkaline metal hydroxide in the presence of enough oxygen to transform (1) substantially completely metallic tin into an alkali metal stannate salt, and (2) stannous sulphide into an alkali metal stannate salt and. a salt of alkali metal, tin and sulphur; and precipitating a tin compound rom tl 1 is solution.

2. The process according to claim 1, characterized in that the period during which said ore material is heated and the temperature at which it is heated are such that the formation of other metals adapted to alloy with tin is rninimizecl.

3. The process accordng to claim 1, characterized in that the solution pregnant with tin is reacted with a metal oxide selected from the group consisting of calcium oxide and barium oxide to precipitate a t c p 4. The process according to claim 1, in that the solution pregnant with tin is reacted with a metal oxide selected from the group consisting of calcium oxide and barium oxide to precipitate a tin compound, regenerating at the Same time the alkaline metal hydroxide solution, separating the precipitate and the solution, and re-using the said solution to leach the cooled reduced ore.

5. The process according to claim 1, characterized in that the solution pregnant with tin is reacted with calcium oxide te precipitate calcium stannate, the precipitation step being conducted in the presence of an eXcess of previously precipitated calcium stannate.

6. The process according to claim 1, characterized in that the solution pregnant with tin is subjected to neutralization by an acid reagent chosen from the group consisting of CO2 and S02 f0 precipitating a tin ccmpound out of the pregnant solution, separating the precipitate and soluton, and regeneratng the solution with a controlled amount of lime.

GREGOIRE GU'IZEIT. ELLIOTT J. ROBERTS. ROBERT B. THOMPSON. 

